2-allyl-2-(prop-2-yn-1-yl)propane-1,3-diol | 113950-93-9

• 分子结构分类: 有机化合物 - 乙炔化物
• 英文名称: 2-allyl-2-(prop-2-yn-1-yl)propane-1,3-diol
• 英文别名: 4,4-bis(hydroxymethyl)-hept-6-en-1-yne；2-Prop-2-enyl-2-prop-2-ynylpropane-1,3-diol
• CAS: 113950-93-9
• 化学式: C₉H₁₄O₂
• 分子量: 154.209
• InChiKey: SYTGEJWHOCLPBO-UHFFFAOYSA-N

物化性质

• 沸点：
  82-87 °C(Press: 0.05-0.07 Torr)
• 密度：
  1.021±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.7
• 重原子数：
  11
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  40.5
• 氢给体数：
  2
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2-allyl-2-(prop-2-yn-1-yl)propane-1,3-diol 在 正丁基锂 、 sodium hydride 作用下， 以 四氢呋喃 为溶剂， 生成 4,4-bis[(benzyloxy)methyl]-7-(trimethylsilyl)-1-hepten-6-yne
  参考文献：
  名称：

  Aldehyde Addition and Copper-Mediated Allylation of Bicyclic Alkoxytitanacyclopentenes and -Pentadienes:  New Selectivities and an Unusual Reaction

  摘要：

  Bicyclic titanacyclopentenes generated in situ from 1,6-enynes and (eta(2)-propene)Ti(O-i-Pr)(2) (1) reacted with aldehydes at their alkenyl-titanium bond in the absence or presence of Ti(O-i-Pr)(n)Cl(4-n) (n = 2 or 3) to give allyl alcohols such as 5-7 as a nearly single stereoisomer in good yields. Upon workup with DCl/D(2)O or iodine, deuterio and iodo derivatives, 8 and 9, were obtained. Bicyclic titanacyclopentadienes prepared analogously from 1,6- or 1,7-diynes and 1 also reacted with aldehydes in the presence of an additional equivalent of Ti(O-i-Pr)(2)Cl(2) to afford 1,2-dialkylidenecyclopentanes pr -cyclohexanes having an alcohol moiety in their side chain in good yields. In place of the simple hydrolysis, deuteriolysis or iodinolysis gave the corresponding derivatives such as 21 or 22. Treatment of 1,6-enyne 10 with 1 in the standard way and then with a slight excess of i-PrMgCl at -50 degrees C generated a new titanium species that, upon reaction with aldehydes, afforded unexpected adducts 34 and 41-45 virtually as a single isomer. Copper-mediated allylation of dialkoxytitanacyclopentene such as 3 with allyl bromide proceeded at their vinyl-titanium bond to give 48 and 50. Likewise, dialkoxytitanacyclopentadiene prepared from 29 and 1 underwent the regioselective copper-mediated mono-allylation to give a 9:1 mixture of 53 and 54. Upon workup with deuteriochloric acid, the corresponding deuterated product was obtained with a high degree of deuterium incorporation.

  DOI：

  10.1021/ja982501e
• 作为产物：
  描述：

  烯丙基丙二酸二甲酯 在 lithium aluminium tetrahydride 、 caesium carbonate 作用下， 以 四氢呋喃 、 丙酮 为溶剂， 反应 18.0h， 生成 2-allyl-2-(prop-2-yn-1-yl)propane-1,3-diol
  参考文献：
  名称：

  铁催化的1,6-烯炔烃的氢硼化环化反应

  摘要：

  用铁制环：我们报道了第一个Fe催化的硼化环化反应，该反应提供一个C-C和一个C-B键，从而允许形成可进一步官能化的含硼基单元的碳环和杂环。该反应在温和的条件下进行，具有廉价的催化体系和充分的原子经济性。机理研究表明，Fe II-氢化物活性催化剂能够在烯烃插入之前与炔烃基团发生中间反应，计算研究表明，沿催化循环发生涉及HBpin和Fe-C键的无障碍σ键易位。

  DOI：

  10.1002/chem.201704401

文献信息

• Catalytic Generation of Rhodium Silylenoid for Alkene–Alkyne–Silylene [2 + 2 + 1] Cycloaddition
  作者：Toshimichi Ohmura、Ikuo Sasaki、Michinori Suginome

  DOI：10.1021/acs.orglett.9b00326

  日期：2019.3.15

  2 + 1] cycloaddition takes place in the rhodium-catalyzed reaction of 1,6-enynes with borylsilanes bearing an alkoxy group on the silicon atoms, which react as synthetic equivalents of silylene. The reaction proceeds efficiently in 1,2-dichloroethane at 80–110 °C in the presence of a rhodium catalyst bearing bis(diphenylphosphino)methane (DPPM) as a ligand to afford 1-silacyclopent-2-enes in good to

  烯烃-炔烃-亚甲基[2 + 2 +1]的环加成反应是在铑催化的1,6-炔烃与在硅原子上带有烷氧基的硼烷基硅烷的反应中进行的，这些硅烷作为合成的甲硅烷基等效物进行反应。在载有双（二苯基膦基）甲烷（DPPM）作为配体的铑催化剂存在下，反应在80-110°C的1,2-二氯乙烷中有效进行，从而以高收率或高收率得到1-silacyclopent-2-enes。
• Rhodium-Catalyzed Silylcarbocyclization (SiCaC) and Carbonylative Silylcarbocyclization (CO−SiCaC) Reactions of Enynes
  作者：Iwao Ojima、An T. Vu、Seung-Yub Lee、James V. McCullagh、Andrew C. Moralee、Masaki Fujiwara、Tram H. Hoang

  DOI：10.1021/ja0258982

  日期：2002.8.1

  of a 1,6-enyne with a hydrosilane catalyzed by Rh(acac)(CO)(2), Rh(4)(CO)(12), or Rh(2)Co(2)(CO)(12) under ambient CO atmosphere or N(2) gives 2-methyl-1-silylmethylidene-2-cyclopentane or its heteroatom congener in excellent yield through silylcarbocycization (SiCaC) process. The same reaction, but in the presence of a phosphite such as P(OEt)(3) and P(OPh)(3) under 20 atm of CO, affords the corresponding

  由 Rh(acac)(CO)(2)、Rh(4)(CO)(12) 或 Rh(2)Co(2)(CO)(12) 催化的 1,6-烯炔与氢硅烷的反应) 在环境 CO 气氛或 N(2) 下通过甲硅烷基碳环化 (SiCaC) 过程以优异的产率得到 2-甲基-1-甲硅烷基亚甲基-2-环戊烷或其杂原子同系物。相同的反应，但在亚磷酸酯如 P(OEt)(3) 和 P(OPh)(3) 的存在下，在 20 个大气压的 CO 下，提供相应的 2-formylmethyl-1-silylmethylidene-2-cyclopentane 或其通过羰基化甲硅烷基碳环化 (CO-SiCaC) 工艺获得具有优异选择性的杂原子同系物。SiCaC 反应也已应用于带有环己烯基作为烯烃部分的 1,6-烯炔和 1,7-烯炔系统。通过这些新型环化反应获得的官能化五元和六元环系统可用作合成天然和非天然杂环和碳环化合物的有用且通用的中间体。讨论了
• Ruthenium Carbene-Mediated Construction of Strained Allenes via the Enyne Cross-Metathesis/Cyclopropanation of 1,6-Enynes
  作者：Ming Gao、Qiangqiang Gao、Xiangbin Hao、Ying Wu、Qingmin Zhang、Guohua Liu、Rui Liu

  DOI：10.1021/acs.orglett.9b04662

  日期：2020.2.7

  Herein, we report on the unprecedented dimerization of 1,6-enynes using a commercially available ruthenium complex RuCl2(PPh3)3, which results in a series of bicyclo[3.1.0]hexyl allene derivatives in moderate to excellent yields. Mechanistic investigation indicates that the in-situ-generated ruthenium vinylidene undergoes a site-selective metathesis process to provide allenyl ruthenium carbene, which

  在本文中，我们报道了使用可商购的钌络合物RuCl2（PPh3）3进行的1,6-烯炔空前的二聚化，结果以中等至极好的收率得到了一系列双环[3.1.0]己基烯丙烯衍生物。机理研究表明，原位生成的亚乙烯基钌经历了位点选择性复分解过程，以提供烯丙基钌卡宾，该烯基可以通过[2 + 2]环加成/金属消除而被烯炔的悬垂C = C键分子内捕获处理。
• Atom-Economical Ni-Catalyzed Diborylative Cyclization of Enynes: Preparation of Unsymmetrical Diboronates
  作者：Natalia Cabrera-Lobera、M. Teresa Quirós、William W. Brennessel、Michael L. Neidig、Elena Buñuel、Diego J. Cárdenas

  DOI：10.1021/acs.orglett.9b02485

  日期：2019.8.16

  We report a Ni-catalyzed diborylative cyclization of enynes that affords carbo- and heterocycles containing both alkyl- and alkenylboronates. The reaction is fully atom-economical, shows a broad scope, and employs a powerful and inexpensive catalytic Ni-based system. The reaction mechanism seems to involve activation of the enyne by Ni(0) through oxidative cyclometalation of the enyne prior to diboron

  我们报告了炔烃的Ni催化的二硼化环化反应，提供了含有烷基硼酸和烯基硼酸的碳环和杂环。该反应是完全原子经济的，显示出广泛的范围，并采用了功能强大且廉价的催化镍基体系。反应机理似乎涉及在乙硼烷试剂活化之前，通过乙炔的氧化环金属化作用，通过Ni（0）活化烯炔。分离出了前所未有的双核双（有机金属）Ni（I）中间配合物。
• (Pentamethylcyclopentadienyl)Iridium Dichloride Dimer {[IrCp*Cl2]2}: A Novel Efficient Catalyst for the Cycloisomerizations of Homopropargylic Diols and N-Tethered Enynes
  作者：Erica Benedetti、Antoine Simonneau、Alexandra Hours、Hani Amouri、Andrea Penoni、Giovanni Palmisano、Max Malacria、Jean-Philippe Goddard、Louis Fensterbank

  DOI：10.1002/adsc.201100124

  日期：2011.8

  iridium dichloride dimer [IrCp*Cl2]2}-catalyzed hydroalkoxylation of bis-homopropargylic alcohols provides an efficient access to dioxabicyclo[2.2.1]ketals. The cycloisomerizations proceed under mild conditions, with low catalytic loadings and short reaction times. This new protocol involving an Ir(III) catalyst also promoted the cycloisomerization of nitrogen-tethered 1,6-enynes to give azabicyclo[4

  （五甲基环戊二烯基）二氯化铱二聚体[[IrCp * Cl 2 ] 2 }催化的双均炔丙醇的加氢烷氧基化反应可有效地获得二氧杂双环[2.2.1]缩酮。环异构化反应在温和的条件下进行，催化负荷低，反应时间短。这项涉及Ir（III）催化剂的新方案还促进了氮系1,6-炔烃的环异构化反应，形成了氮杂双环[4.1.0]庚烯，从而提高了我们方法的合成潜力。